JPH07126230A - Di-long-chain type tertiary amine acid salt particle and its production - Google Patents
Di-long-chain type tertiary amine acid salt particle and its productionInfo
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- JPH07126230A JPH07126230A JP29447393A JP29447393A JPH07126230A JP H07126230 A JPH07126230 A JP H07126230A JP 29447393 A JP29447393 A JP 29447393A JP 29447393 A JP29447393 A JP 29447393A JP H07126230 A JPH07126230 A JP H07126230A
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- Japan
- Prior art keywords
- tertiary amine
- chain type
- long
- type tertiary
- acid salt
- Prior art date
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は衣料用柔軟仕上げ剤に有
用な柔軟剤基剤であるジ長鎖型第３級アミン酸塩粒子及
びその製造方法に関する。更に詳しくは、流動性が良好
で且つ水中での分散性及び溶解性の優れたジ長鎖型第３
級アミン酸塩粒子の粉末の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a di-long chain type tertiary amine acid salt particle which is a softening agent base useful as a softening agent for clothing and a method for producing the same. More specifically, the di-long chain type third compound having good fluidity and excellent dispersibility and solubility in water.
The present invention relates to a method for producing a powder of primary amine acid salt particles.
【０００２】[0002]
【従来の技術・発明が解決しようとする課題】ジ長鎖型
第３級アミン酸塩は良好な柔軟性能、低刺激性、良生分
解性と言った特質を有し、粉末化して用いることが要望
されていた。この粉末化の方法としては、ジ長鎖型第３
級アミン酸塩単体を粉末化する方法もあるが、単体では
粉末柔軟剤としての水中への分散性、溶解性に問題があ
ると共にそれに伴い十分な柔軟性が発現しないという問
題がある。また、特開昭６３−１３８０００号公報は、
溶解性を改良する技術として吸油担体に柔軟基剤を吸着
させた形態を特徴としているが、有効成分の含有量が少
なく、濃縮化粉末柔軟剤を設計する上で十分でない。
又、特開昭６２−２５３６９８号公報は顆粒状柔軟剤組
成物として１５０μｍ以下のジ長鎖アルキル４級アンモ
ニウム塩粉体と発泡性組成物の造粒により溶解性を改良
しようとするものであるが、水中分散後の１次粒子の溶
解性向上には効果が見られない。2. Description of the Related Art Di-long-chain type tertiary amine acid salt has characteristics such as good softness, low irritation and good biodegradability, and it should be used in the form of powder. It was requested. This powdering method includes di-long chain type third
There is also a method of powdering the primary amine acid salt simple substance, but there is a problem that the simple substance alone has a problem in dispersibility and solubility in water as a powder softening agent, and accordingly, sufficient flexibility is not expressed. Further, Japanese Patent Laid-Open No. 63-138000 discloses
As a technique for improving the solubility, it is characterized by a form in which a soft base is adsorbed on an oil absorption carrier, but the content of the active ingredient is small, which is not sufficient for designing a concentrated powder softener.
Further, JP-A-62-253698 is intended to improve the solubility by granulating a foaming composition with a dilong chain alkyl quaternary ammonium salt powder having a particle size of 150 μm or less as a granular softener composition. However, no effect is seen in improving the solubility of the primary particles after dispersion in water.
【０００３】又、特開昭５７−１９３５７４号公報に
は、水を必須条件とする液体混合物を固体粒子に変える
ことを特徴とする製造方法があるが、ジ長鎖型第３級ア
ミン酸塩は水の共存下では加水分解を起こすという問題
がある。Further, Japanese Patent Application Laid-Open No. 57-193574 discloses a production method characterized in that a liquid mixture in which water is an essential condition is changed into solid particles. Has a problem that it causes hydrolysis in the presence of water.
【０００４】本発明は、このような従来技術の問題点に
着目してなされたものであり、溶解助剤をジ長鎖型第３
級アミン化合物又はジ長鎖型第３級アミン酸塩と溶融状
態でミクロ混合し、粉末化することにより流動性が良好
で且つ水中での分散性及び溶解性の優れたジ長鎖型第３
級アミン酸塩の粉末を効率よく得ることのできる製造方
法を提供することを目的としている。また、本発明は、
このような製造方法により得られるジ長鎖型第３級アミ
ン酸塩粒子を提供することを目的とする。The present invention has been made by paying attention to the problems of the prior art as described above.
Micro-mixing with a tertiary amine compound or a di-long-chain type tertiary amine acid salt in a molten state and powdering the di-long-chain type third compound having good fluidity and excellent dispersibility and solubility in water.
It is an object of the present invention to provide a production method capable of efficiently obtaining a powder of a primary amine salt. Further, the present invention is
It is an object of the present invention to provide dilong-chain type tertiary amine acid salt particles obtained by such a production method.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、溶融させ
たジ長鎖型第３級アミン酸塩と溶解助剤を溶融混合する
或いは、溶融させたジ長鎖型第３級アミン化合物と溶解
助剤を溶融混合した後に酸と中和反応させ、次いで粉末
化させる事によりジ長鎖型第３級アミン酸塩の粒子が容
易に得られることに着目して鋭意研究を行い、本発明を
完成するに至った。Means for Solving the Problems The inventors of the present invention melt-mixed a melted di-long-chain type tertiary amine acid salt and a dissolution aid, or melted the melted di-long-chain type tertiary amine compound. We conducted intensive research focusing on the fact that the particles of the di-long-chain type tertiary amine acid salt can be easily obtained by performing a neutralization reaction with an acid and then pulverizing it after melt-mixing The invention was completed.
【０００６】即ち、本発明の要旨は、（１）ジ長鎖型第
３級アミン化合物と酸をジ長鎖型第３級アミン化合物の
融点ないし沸点の温度範囲で中和反応を行い、得られた
ジ長鎖型第３級アミン酸塩と溶解助剤をジ長鎖型第３級
アミン酸塩の融点ないし沸点の温度範囲で溶融混合し、
次いで粉末化することを特徴とするジ長鎖型第３級アミ
ン酸塩粒子の製造方法、（２）ジ長鎖型第３級アミン化
合物と溶解助剤をジ長鎖型第３級アミン化合物の融点な
いし沸点の温度範囲で溶融混合した後、該温度範囲で酸
と中和反応させ、次いで粉末化することを特徴とするジ
長鎖型第３級アミン酸塩粒子の製造方法、（３）ジ長鎖
型第３級アミン酸塩１００重量部に対して溶解助剤を１
〜１００重量部含有し、且つ重量平均粒子径が５０〜１
０００μｍで、見掛け比重が１５０〜１２００ｇ／リッ
トルである、前記（１）又は（２）記載の方法により製
造されるジ長鎖型第３級アミン酸塩粒子、に関する。That is, the gist of the present invention is to obtain (1) a neutralization reaction between a dilong-chain type tertiary amine compound and an acid within the temperature range of the melting point or boiling point of the dilong-chain type tertiary amine compound. The obtained di-long-chain type tertiary amine acid salt and a dissolution aid are melt-mixed in a temperature range of the melting point or boiling point of the di-long-chain type tertiary amine acid salt,
Then, a method for producing di-long chain type tertiary amine acid salt particles, which comprises pulverizing, (2) di-long chain type tertiary amine compound and a dissolution aid A method for producing particles of a di-long-chain type tertiary amine acid salt, which comprises melt-mixing in a temperature range from the melting point to the boiling point of, and neutralizing with an acid in the temperature range, and then pulverizing. ) 1 part of the dissolution aid is added to 100 parts by weight of the di-long-chain type tertiary amine acid salt.
To 100 parts by weight and a weight average particle size of 50 to 1
The present invention relates to di-long chain type tertiary amine acid salt particles produced by the method according to the above (1) or (2), which has an apparent specific gravity of 150 to 1200 g / liter.
【０００７】以下、本発明を詳細に説明する。本発明に
用いられるジ長鎖型第３級アミン化合物としては、特に
限定されるものではなく、例えば下記の（Ａ−１）、
（Ａ−２）又は（Ａ−３）で表される化合物等を挙げる
ことができる。The present invention will be described in detail below. The di-long chain type tertiary amine compound used in the present invention is not particularly limited, and for example, the following (A-1),
The compound etc. which are represented by (A-2) or (A-3) can be mentioned.
【０００８】[0008]
【化１】 [Chemical 1]
【０００９】（式中、Ｒ1 は炭素数１〜４のアルキル基
又はヒドロキシアルキル基を、Ｒ2及びＲ3 は同一又は
相異なって炭素数１１〜２１のアルキル基又はアルケニ
ル基を、Ｒ4 は炭素数１２〜２２のアルキル基又はアル
ケニル基を表す。ｍは２又は３である。）(Wherein R 1 is an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms, R 2 and R 3 are the same or different and are alkyl groups or alkenyl groups having 11 to 21 carbon atoms, R 4 Represents an alkyl group or an alkenyl group having 12 to 22 carbon atoms, and m is 2 or 3.)
【００１０】本発明の製造方法においてこれらのジ長鎖
型第３級アミン化合物は、単一で、あるいは２種以上を
混合して用いることができる。これらの化合物の合成方
法は、いずれも特に限定されるものではなく、以下の方
法に準じて合成することができる。即ち、（Ａ−１）で
表される化合物は、例えば、Ｎ−低級アルキルアルカノ
ールアミンやジエタノールアミン等のジアルカノールア
ミンのシアノエチル化、水添反応により得られる次式
（ＡＢ−１）で表される化合物を炭素数１２〜２２の脂
肪酸と反応させることにより得ることができる。In the production method of the present invention, these di-long chain type tertiary amine compounds may be used alone or in admixture of two or more. The method for synthesizing these compounds is not particularly limited, and they can be synthesized according to the following methods. That is, the compound represented by (A-1) is represented by the following formula (AB-1) obtained by, for example, cyanoethylation of a dialkanolamine such as N-lower alkylalkanolamine or diethanolamine, and a hydrogenation reaction. It can be obtained by reacting a compound with a fatty acid having 12 to 22 carbon atoms.
【００１１】[0011]
【化２】 [Chemical 2]
【００１２】（式中、Ｒ1 及びｍは前記と同じ意味を表
す。）(In the formula, R 1 and m have the same meanings as described above.)
【００１３】また、（Ａ−２）で表される化合物は、例
えば、Ｎ−低級アルキルジエタノールアミンの分子内脱
水環化反応により得られる次式（ＡＢ−２）で表される
化合物を脂肪族アミンと開環アミド化反応させた後、炭
素数１２〜２２の脂肪酸ハライドと反応させ、得られた
化合物を水酸化ナトリウム等のアルカリ溶液で洗浄する
ことにより得ることができる。Further, the compound represented by the formula (A-2) is, for example, a compound represented by the following formula (AB-2) obtained by an intramolecular dehydration cyclization reaction of N-lower alkyldiethanolamine with an aliphatic amine. After a ring-opening amidation reaction with, a reaction with a fatty acid halide having 12 to 22 carbon atoms and washing the obtained compound with an alkaline solution such as sodium hydroxide can be obtained.
【００１４】[0014]
【化３】 [Chemical 3]
【００１５】（式中、Ｒ1 は前記と同じ意味を表す。）(In the formula, R 1 has the same meaning as described above.)
【００１６】更に、（Ａ−３）で表される化合物は、例
えば、Ｎ−高級アルキル又はアルケニルジエタノールア
ミンの脱水環化反応により得られる次式（ＡＢ−３）で
表される化合物を低級アルキルアミンと反応させた後、
炭素数１２〜２２の脂肪酸ハライドと反応させ、得られ
た化合物を水酸化ナトリウム等のアルカリ溶液で洗浄す
ることにより得ることができる。Further, the compound represented by the formula (A-3) is, for example, a compound represented by the following formula (AB-3) obtained by a dehydration cyclization reaction of an N-higher alkyl or alkenyldiethanolamine with a lower alkylamine. After reacting with
It can be obtained by reacting with a fatty acid halide having 12 to 22 carbon atoms and washing the obtained compound with an alkaline solution such as sodium hydroxide.
【００１７】[0017]
【化４】 [Chemical 4]
【００１８】（式中、Ｒ4 は前記と同じ意味を表す。）(In the formula, R 4 has the same meaning as described above.)
【００１９】本発明に用いられる酸としては、無機酸又
は有機酸のいずれも用いることができ、無機酸としては
例えば塩酸、硫酸、硝酸、燐酸等が挙げられ、有機酸と
しては例えば酢酸、グリコール酸、クエン酸、コハク
酸、乳酸等の炭素数１〜６の有機酸が挙げられる。これ
らの酸のうち、酸のコスト及び得られるジ長鎖型第３級
アミン酸塩の粉末の柔軟性、保存安定性、匂い等の点か
ら塩酸、燐酸、又はグリコール酸が好ましい。これらの
酸は、単一の酸で或いは２種以上の混酸で用いることが
できる。As the acid used in the present invention, either an inorganic acid or an organic acid can be used. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like, and examples of the organic acid include acetic acid and glycol. Examples thereof include organic acids having 1 to 6 carbon atoms such as acid, citric acid, succinic acid and lactic acid. Among these acids, hydrochloric acid, phosphoric acid, or glycolic acid is preferable from the viewpoints of cost of the acid and flexibility of the obtained powder of the di-long-chain type tertiary amine acid salt, storage stability, odor and the like. These acids can be used as a single acid or as a mixed acid of two or more kinds.
【００２０】本発明においては、酸として溶媒を含まな
い酸を用いる態様と酸を溶媒に溶解させて酸の溶液とし
て用いる態様とがある。溶媒を含んだ状態で用いる後者
では、溶媒として、水、炭素数１〜６の低級アルコー
ル、炭素数４〜８の脂肪族及び芳香族炭化水素等が用い
られる。市販品の多くは、酸が水に溶解したものであ
り、本発明ではこれらの中でできるだけ濃度の高いもの
を用いるのが好ましい。これらの溶媒は、後述の如く溶
媒の除去工程により中和物から除去される。一方、溶媒
を含まない形態で使用する前者の場合は、溶媒を除去す
る工程は不要となる。In the present invention, there are a mode in which an acid containing no solvent is used as an acid and a mode in which the acid is dissolved in a solvent and used as a solution of the acid. In the latter used in the state of containing a solvent, water, a lower alcohol having 1 to 6 carbon atoms, an aliphatic or aromatic hydrocarbon having 4 to 8 carbon atoms, etc. are used as the solvent. Most of the commercially available products are those in which an acid is dissolved in water, and in the present invention, it is preferable to use the one having the highest concentration among them. These solvents are removed from the neutralized product in the solvent removal step as described below. On the other hand, in the former case of using the solvent-free form, the step of removing the solvent is unnecessary.
【００２１】本発明においては、酸の使用量は、中和等
価量に対して０．５０〜２．００倍が好ましく、より好
ましくは０．７５〜１．５０倍である。０．５０倍より
少ないと柔軟性能が低下し好ましくない。２．００倍を
越えると、酸成分が過剰に残り柔軟剤基剤としては好ま
しくなく、また色相の劣化が生じる。In the present invention, the amount of the acid used is preferably 0.50 to 2.00 times, more preferably 0.75 to 1.50 times the neutralization equivalent amount. If it is less than 0.50 times, the flexibility performance is deteriorated, which is not preferable. If it exceeds 2.00 times, the acid component will remain in excess, which is not preferable as a softener base, and the hue will deteriorate.
【００２２】本発明で用いられる溶解助剤としては、ジ
長鎖型第３級アミン酸塩の水への分散性、溶解性又は基
剤自身の崩壊性を向上させるものであれば、特に限定さ
れるものではなく、例えば次のようなものが挙げられ
る。 （１）非イオン界面活性剤 例えばポリオキシエチレンアルキルエーテル（酸化エチ
レン：５〜５０モル、アルキル基の炭素数：１２〜２
４）、ポリオキシエチレンアルケニルエーテル（酸化エ
チレン：５〜５０モル、アルケニル基の炭素数：１２〜
２４）、ポリオキシエチレンアルケニルアミン（酸化エ
チレン：５〜５０モル、アルケニル基の炭素数：１２〜
２４）等が挙げられる。また、これらの化合物の酸化エ
チレンの代わりに酸化プロピレンを用いた物質及び酸化
エチレンと酸化プロピレンの混合物を用いた物質も同様
に好適に用いることができる。The solubilizing agent used in the present invention is not particularly limited as long as it improves the dispersibility, solubility, or disintegration of the base itself of the dilong-chain type tertiary amine acid salt in water. However, the following may be mentioned, for example. (1) Nonionic surfactant For example, polyoxyethylene alkyl ether (ethylene oxide: 5 to 50 mol, carbon number of alkyl group: 12 to 2)
4), polyoxyethylene alkenyl ether (ethylene oxide: 5 to 50 mol, carbon number of alkenyl group: 12 to 12)
24), polyoxyethylene alkenylamine (ethylene oxide: 5 to 50 mol, carbon number of alkenyl group: 12 to 12)
24) and the like. Further, a substance using propylene oxide instead of ethylene oxide of these compounds and a substance using a mixture of ethylene oxide and propylene oxide can be similarly suitably used.
【００２３】（２）多価アルコール 例えばグリセリン、トリメチロールプロパン、ペンタエ
リスリトール、ソルビトール等の３〜６価の多価アルコ
ールが挙げられる。 （３）長鎖脂肪酸及びそのエステル化合物 例えばラウリン酸、オレイン酸、ステアリン酸、硬化牛
脂脂肪酸等の炭素数８〜２２の長鎖脂肪酸及びそのエス
テル化合物が挙げられる。エステル化合物としては、こ
れらの長鎖脂肪酸と上記多価アルコールとのエステル
が、より好ましい。また、そのエステル化合物の水酸基
に酸化エチレン及び／又は酸化プロピレンを２〜８０モ
ル付加させた化合物を用いることもできる。(2) Polyhydric alcohol Examples thereof include trihydric and trihydric polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol and sorbitol. (3) Long-chain fatty acid and ester compound thereof For example, long-chain fatty acid having 8 to 22 carbon atoms such as lauric acid, oleic acid, stearic acid, and hardened beef tallow fatty acid and ester compound thereof can be mentioned. As the ester compound, esters of these long-chain fatty acids and the above polyhydric alcohols are more preferable. Further, a compound obtained by adding 2 to 80 mol of ethylene oxide and / or propylene oxide to the hydroxyl group of the ester compound can also be used.
【００２４】（４）無機塩及び無機物 例えば炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリ
ウム、塩化ナトリウム等のアルカリ金属塩、炭酸カルシ
ウム、炭酸マグネシウム等のアルカリ土類金属塩や尿素
及びその誘導体等の無機物が挙げられる。 （５）有機酸及び有機塩 例えばグリコール酸、フマル酸、パラトルエンスルホン
酸ナトリウム等が挙げられる。(4) Inorganic salts and inorganic substances For example, alkali metal salts such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and sodium chloride, alkaline earth metal salts such as calcium carbonate and magnesium carbonate, and inorganic substances such as urea and its derivatives. Can be mentioned. (5) Organic acids and organic salts For example, glycolic acid, fumaric acid, sodium paratoluenesulfonate, etc. may be mentioned.
【００２５】（６）有機高分子 例えばポリビニルアルコール、カルボキシメチルセルロ
ース、スノーアルギン酸ナトリウム、ポリアクリル酸ナ
トリウム等が挙げられる。 （７）粘土鉱物 例えば含水ケイ酸マグネシウム・リチウム、ベントナイ
ト、シリカ等が挙げられる。(6) Organic Polymers Examples thereof include polyvinyl alcohol, carboxymethyl cellulose, sodium snow alginate, sodium polyacrylate and the like. (7) Clay mineral Examples include hydrous magnesium silicate / lithium, bentonite, silica and the like.
【００２６】本発明においては、これらから選ばれる１
種または２種以上の混合物を溶解助剤として用いる。ま
た、溶解助剤の添加量としては、ジ長鎖型第３級アミン
酸塩１００重量部に対して、通常１〜１００重量部、好
ましくは５〜３０重量部である。添加量が１００重量部
を越えても、それに見合う溶解促進効果はなく、逆にジ
長鎖型第３級アミン酸塩に対する溶解助剤の量が多くな
りすぎて、柔軟仕上剤としての組成設計上の制約が大と
なり好ましくなく、１重量部より少ないと充分な効果が
得られない。In the present invention, 1 selected from these is selected.
One kind or a mixture of two or more kinds is used as a dissolution aid. The addition amount of the solubilizing agent is usually 1 to 100 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the di-long chain type tertiary amine acid salt. Even if the added amount exceeds 100 parts by weight, there is no corresponding dissolution promoting effect, and conversely, the amount of the dissolution aid with respect to the di-long-chain type tertiary amine acid salt becomes too large, and the composition design as a softening agent is designed. This is not preferable because the above restriction becomes large, and if it is less than 1 part by weight, a sufficient effect cannot be obtained.
【００２７】溶解助剤の添加方法は、中和の前又は後に
供給する方法である。ジ長鎖型第３級アミン化合物ある
いはジ長鎖型第３級アミン酸塩と溶融混合させることに
よって流動性が良好で且つ水中での分散性及び溶解性が
従来の柔軟基剤に比べてより優れたジ長鎖型第３級アミ
ン酸塩の粉末を得ることができる。The solubilizing agent is added before or after the neutralization. By melt-mixing with a di-long-chain type tertiary amine compound or a di-long-chain type tertiary amine acid salt, the fluidity is good and the dispersibility and solubility in water are better than those of conventional soft bases. It is possible to obtain an excellent powder of a di-long-chain type tertiary amine acid salt.
【００２８】本発明の製造方法では、以上の原料を用い
て中和反応及び溶解助剤との溶融混合を行うが、本発明
は特定の温度範囲で温度を制御しながら中和反応及び溶
融混合することを特徴とする。ここで中和反応及び溶融
混合の温度は、中和反応後に溶解助剤を添加する場合
は、ジ長鎖型第３級アミン化合物と酸をジ長鎖型第３級
アミン化合物の融点ないし沸点の温度範囲で中和反応を
行い、得られたジ長鎖型第３級アミン酸塩の融点ないし
沸点の温度範囲で溶解助剤をジ長鎖型第３級アミン酸塩
と溶融混合する。また、中和反応前に溶解助剤を添加す
る場合は、ジ長鎖型第３級アミン化合物と溶解助剤をジ
長鎖型第３級アミン化合物の融点ないし沸点の温度範囲
で溶融混合した後、該温度範囲で酸と中和反応させる。In the production method of the present invention, the above raw materials are used for the neutralization reaction and the melt mixing with the solubilizing agent. In the present invention, the neutralization reaction and the melt mixing are performed while controlling the temperature in a specific temperature range. It is characterized by doing. Here, the temperature of the neutralization reaction and the melt mixing are such that, when a dissolution aid is added after the neutralization reaction, the di-long chain type tertiary amine compound and the acid are the melting point or boiling point of the di-long chain type tertiary amine compound. The neutralization reaction is carried out in the temperature range of 1. and the dissolution aid is melt-mixed with the di-long chain type tertiary amine acid salt in the temperature range of the melting point or boiling point of the obtained di-long chain type tertiary amine acid salt. When the dissolution aid is added before the neutralization reaction, the dilong-chain type tertiary amine compound and the dissolution aid are melt-mixed within the temperature range from the melting point to the boiling point of the dilong-chain type tertiary amine compound. After that, it is neutralized with an acid in the temperature range.
【００２９】いずれの場合でも通常、ジ長鎖型第３級ア
ミン化合物又はジ長鎖型第３級アミン酸塩の融点ないし
沸点の温度範囲であり、好ましくは融点より１５℃高い
温度ないし沸点より２０℃低い温度範囲である。ジ長鎖
型第３級アミン化合物又はジ長鎖型第３級アミン酸塩の
沸点を越えると分解を起こしてしまう。一方、融点より
低い温度では、ジ長鎖型第３級アミン化合物又はジ長鎖
型第３級アミン酸塩が固化してしまうため酸及び溶解助
剤との均一な中和や混合ができなくなり、目的とする中
和物を得ることが困難になる。In any case, it is usually in the temperature range of the melting point or boiling point of the dilong-chain type tertiary amine compound or the dilong-chain type tertiary amine acid salt, preferably 15 ° C higher than the melting point or higher than the boiling point. The temperature range is 20 ° C. lower. If the boiling point of the di-long chain type tertiary amine compound or the di-long chain type tertiary amine acid salt is exceeded, decomposition will occur. On the other hand, at a temperature lower than the melting point, the di-long-chain type tertiary amine compound or the di-long-chain type tertiary amine acid salt is solidified, so that the acid and the dissolution aid cannot be uniformly neutralized or mixed. It becomes difficult to obtain the target neutralized product.
【００３０】中和反応及び溶解助剤との溶融混合に用い
る反応器としては、特に限定されず、バッチ式、連続式
いずれでもよいが、均一な混合が可能な管型反応器（Ｐ
ＦＲ）又は１槽あるいは多段の連続攪拌槽式反応器（Ｃ
ＳＴＲ）が、より好適に用いられる。ＰＦＲとしては、
ノリタケカンパニー製のスタティックミキサーの様な静
止型、（株）エバラ製作所製のマイルダーの様な高剪断
型、また循環ポンプを有するループリアクター等が挙げ
られる。また、１槽あるいは多段のＣＳＴＲとしては、
攪拌機を有する公知の反応槽を用いることができる。The reactor used for the neutralization reaction and the melt mixing with the solubilizing agent is not particularly limited, and may be a batch type or a continuous type, but a tubular reactor (P
FR) or 1 tank or multi-stage continuous stirred tank reactor (C
STR) is more preferably used. As PFR,
Examples include static type such as static mixer manufactured by Noritake Company, high shear type such as Milder manufactured by Ebara Seisakusho, and loop reactor having a circulation pump. Also, as a single tank or multi-stage CSTR,
A known reaction tank having a stirrer can be used.
【００３１】本発明においては、中和及び溶解助剤との
溶融混合等の処理後にジ長鎖型第３級アミン酸塩の粉末
化を行う。この粉末化の方法としては、溶媒を含まない
酸を用いた場合は、中和又は溶解助剤との溶融混合等の
処理後に冷却を行う。本発明で用いられる冷却機として
は、特に限定されるものではなく、例えばベルト或いは
ドラム式クーラー、噴霧冷却塔を用いることが出来る
が、冷却とともに粉末化ができる噴霧冷却方式が望まし
い。In the present invention, the dilong-chain type tertiary amine acid salt is pulverized after treatments such as neutralization and melt mixing with a solubilizing agent. As a method for pulverizing, when an acid containing no solvent is used, cooling is performed after treatment such as neutralization or melt mixing with a dissolution aid. The cooler used in the present invention is not particularly limited, and for example, a belt or drum type cooler and a spray cooling tower can be used, but a spray cooling system capable of powdering with cooling is desirable.
【００３２】また、溶媒を含む酸を用いた場合は、中和
又は溶解助剤との溶融混合等の処理後に乾燥による脱溶
媒及び冷却を行う。乾燥機としては特に限定されること
はないが、例えば薄膜型蒸発機、攪拌式薄膜蒸発機（神
鋼パンテック（株））、フラッシュドライヤー、真空蒸
発缶、カレントドライヤー（（株）大川原製作所）、ス
プレードライヤー（大川原化工機（株））、ループドラ
イヤー（（株）奈良機械製作所）等があげられる。操作
条件としては常圧、真空どちらでもよいが、真空下で顕
熱を利用したフラッシュ脱溶媒方式が効率的である。こ
の場合における圧力は好ましくは５００Ｔｏｒｒ以下、
より好ましくは２００Ｔｏｒｒ以下が良い。又、乾燥機
への供給温度は脱溶媒の効率を高める点からジ長鎖型第
３級アミン酸塩の融点以上が良い。When an acid containing a solvent is used, the solvent is removed by drying and the cooling is performed after the treatment such as the neutralization or the melt mixing with the dissolution aid. Although the dryer is not particularly limited, for example, a thin film evaporator, a stirring thin film evaporator (Shinko Pantech Co., Ltd.), a flash dryer, a vacuum evaporator, a current dryer (Okawara Manufacturing Co., Ltd.), Examples include spray dryers (Okawara Kakohki Co., Ltd.), loop dryers (Nara Machinery Co., Ltd.), and the like. The operating conditions may be either atmospheric pressure or vacuum, but the flash desolvation method utilizing sensible heat under vacuum is effective. In this case, the pressure is preferably 500 Torr or less,
More preferably, it is 200 Torr or less. Further, the temperature of supply to the dryer is preferably higher than the melting point of the dilong-chain type tertiary amine acid salt from the viewpoint of increasing the efficiency of desolvation.
【００３３】冷却に用いる冷却機としては、前記と同様
のものを使用することができるが、乾燥と同時に冷却粉
末化できる場合は冷却工程は不要である。また、乾燥後
のジ長鎖型第３級アミン酸塩に含まれる溶媒の量は粉末
物性、組成安定性から好ましくは５重量％以下、より好
ましくは２重量％以下が望ましい。As the cooler used for cooling, the same one as described above can be used, but if it can be cooled and powdered simultaneously with drying, the cooling step is not necessary. The amount of the solvent contained in the di-long-chain type tertiary amine acid salt after drying is preferably 5% by weight or less, more preferably 2% by weight or less from the viewpoint of powder physical properties and composition stability.
【００３４】本発明の製造方法により得られるジ長鎖型
第３級アミン酸塩粒子は、得られる粉末の流動性、分散
性及び溶解性から重量平均粒子径は好ましくは５０〜１
０００μｍ、より好ましくは１００〜７００μｍが良
い。見掛け比重は好ましくは１５０〜１２００ｇ／リッ
トル、より好ましくは５００〜９００ｇ／リットルが良
い。The di-long-chain type tertiary amine acid salt particles obtained by the production method of the present invention preferably have a weight average particle diameter of 50 to 1 in view of the fluidity, dispersibility and solubility of the obtained powder.
000 μm, and more preferably 100 to 700 μm. The apparent specific gravity is preferably 150 to 1200 g / liter, more preferably 500 to 900 g / liter.
【００３５】[0035]
【実施例】以下、合成例、実施例および比較例により本
発明をさらに詳しく説明するが、本発明はこれらの実施
例等によりなんら限定されるものではない。 合成例１ Ｎ−メチルエタノールアミンとアクリロニトリルの付加
物より公知の方法〔J.Org. Chem., 26, 3409, (1960)]
で合成したＮ−（２−ヒドロキシエチル）−Ｎ−メチル
−１，３−プロピレンジアミン６６ｇと硬化牛脂脂肪酸
２８４ｇを温度計、攪拌機、トラップのついた４つ口フ
ラスコに仕込み、１８０℃まで昇温した。その温度で約
３０分間加熱した。圧力は２００Ｔｏｒｒで行った。次
に圧力を５０Ｔｏｒｒまで下げ８時間加熱を続けた。そ
の結果、前記の一般式（Ａ−１）においてＲ1 がメチ
ル、Ｒ2 及びＲ3 が硬化牛脂脂肪酸残基、ｍが２である
ジ長鎖型第３級アミン化合物を主成分とする反応物３０
０ｇを得た。得られた反応物の酸価、ケン化価、水酸基
価、全アミン価、及び３級アミン価を測定し反応物の組
成を調べた結果、ジ長鎖型第３級アミン化合物が８６重
量％、モノ長鎖型第３級アミンが１２重量％、未反応脂
肪酸が２重量％であった。また、ジ長鎖型第３級アミン
化合物の分子量は６４５、融点は５８〜６５℃、沸点は
２７０〜２７８℃であった。EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. Synthesis Example 1 A method known from the addition product of N-methylethanolamine and acrylonitrile [J. Org. Chem., 26 , 3409, (1960)].
66 g of N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine and 284 g of hardened beef tallow fatty acid synthesized in Step 2 were placed in a 4-neck flask equipped with a thermometer, a stirrer, and a trap, and heated to 180 ° C. did. Heated at that temperature for about 30 minutes. The pressure was 200 Torr. Next, the pressure was reduced to 50 Torr and heating was continued for 8 hours. As a result, in the general formula (A-1), R 1 is methyl, R 2 and R 3 are hardened beef tallow fatty acid residues, and a reaction containing a di-long chain type tertiary amine compound in which m is 2 as a main component Thing 30
0 g was obtained. The acid value, saponification value, hydroxyl value, total amine value, and tertiary amine value of the obtained reaction product were measured and the composition of the reaction product was investigated. As a result, the di-long-chain type tertiary amine compound was 86% by weight. The mono long-chain type tertiary amine was 12% by weight, and the unreacted fatty acid was 2% by weight. The di-long chain type tertiary amine compound had a molecular weight of 645, a melting point of 58 to 65 ° C and a boiling point of 270 to 278 ° C.
【００３６】実施例１ １３０℃に昇温した合成例１で得られたジ長鎖型第３級
アミン化合物と、３５重量％の塩酸水溶液を中和等価量
になるように（株）エバラ製作所製のラボ用マイルダー
に供給し温度を１３０℃に保って中和した。次に、溶融
状態の尿素をジ長鎖型第３級アミン酸塩１００重量部に
対して１０重量部となるように供給し、ジ長鎖型第３級
アミン塩酸塩と尿素をマイルダーで混合した後、次いで
５０〜６０Ｔｏｒｒの圧力下にある真空蒸発缶に供給
し、ジ長鎖型第３級アミン塩酸塩中に含まれる水を蒸発
させた。次いで大川原化工機（株）製のスプレークーラ
ー（ＣＬ型）に供給し、冷却するとともに粉末化させ、
ジ長鎖型第３級アミン塩酸塩の粉末を得た。次いで、得
られたジ長鎖型第３級アミン塩酸塩の粉末の保存安定
性、溶解時間、重量平均粒子径（JIS K 3362）、見掛け
比重（JIS K 3362）及び柔軟性の評価を行った。得られ
た結果を表１に示す。Example 1 Ebara Seisakusho Co., Ltd. was adjusted so that the di-long-chain type tertiary amine compound obtained in Synthesis Example 1 heated to 130 ° C. and a 35% by weight aqueous hydrochloric acid solution would have a neutralization equivalent amount. It was supplied to a laboratory milder manufactured by Kuraray Co., Ltd. and the temperature was kept at 130 ° C. for neutralization. Next, urea in a molten state was supplied so as to be 10 parts by weight with respect to 100 parts by weight of the di-long chain type tertiary amine acid salt, and the di-long chain type tertiary amine hydrochloride and urea were mixed by a milder. After that, it was then fed to a vacuum evaporator under a pressure of 50 to 60 Torr to evaporate the water contained in the dilong-chain type tertiary amine hydrochloride. Next, it is supplied to a spray cooler (CL type) manufactured by Okawara Kakoki Co., Ltd., cooled and pulverized,
A powder of dilong-chain tertiary amine hydrochloride was obtained. Next, the storage stability, dissolution time, weight average particle diameter (JIS K 3362), apparent specific gravity (JIS K 3362) and flexibility of the obtained powder of di-long chain type tertiary amine hydrochloride were evaluated. . The results obtained are shown in Table 1.
【００３７】〔保存安定性の評価法〕200ml のサンプル
瓶に得られた粉末を50ｇ入れ、その上に濾紙(ADVANTEC,
No.3) を置いた。温度30℃、ＲＨ80％の恒温恒湿中に放
置し、20日後にケーキング状態について判定を行った。
ケーキングの状態は下記の三段階で評価した。 ○：流動性良く流れ出る。 △：流れ出るが固まりがある。 ×：出てこない。[Evaluation Method of Storage Stability] 50 g of the obtained powder was put in a 200 ml sample bottle, and filter paper (ADVANTEC,
No.3) was put. The sample was left in a constant temperature and constant humidity of 30 ° C. and RH of 80%, and 20 days later, the caking state was evaluated.
The state of caking was evaluated according to the following three grades. ○: Flows out with good fluidity. Δ: Runs out, but there is a lump. X: Does not appear.
【００３８】〔溶解時間の評価法〕300ml のビーカーに
15℃の水道水200ml を入れ、スターラーで攪拌した状態
で得られた粒子をジ長鎖型第３級アミン酸塩の濃度が 3
3ppmとなるように投入した。ジ長鎖型第３級アミン酸塩
及び水溶性の溶解助剤が溶解して均一な状態になる迄の
時間、又はジ長鎖型第３級アミン酸塩が溶解し、水不溶
性の溶解助剤中に均一に分散するのに要する時間を求め
た。[Evaluation Method of Dissolution Time] In a 300 ml beaker
Add 200 ml of tap water at 15 ℃ and stir with a stirrer to obtain particles with a concentration of dilong-chain type tertiary amine acid salt of 3
It was added so that it would be 3 ppm. The time until the di-long-chain type tertiary amine acid salt and the water-soluble solubilizing agent dissolve into a uniform state, or the time when the di-long-chain type tertiary amine acid salt dissolves and the water-insoluble solubilizing agent is dissolved. The time required for uniform dispersion in the agent was determined.
【００３９】〔柔軟性試験法〕市販の木綿タオルを市販
洗剤アタック（花王株式会社製）にて５回繰り返して洗
濯し、布についている洗剤を除去した後、上記の処理を
した木綿タオル１ｋｇに対して粉末状柔軟剤１ｇの割合
で使用して、３．５°ＤＨ硬水、２５℃、浴比１／３０
にて５分間攪拌処理をした。上記の処理布を室温で風乾
後、２５℃、６５％ＲＨの恒温恒湿室に１日放置した。
上記処理布について、市販柔軟剤（ハミング１／３；花
王株式会社製）で柔軟基剤が同一処理濃度になるように
処理した木綿タオルを対照にして柔軟性について一対比
較を行い、下記の評価基準にて評価した。 ＋２ 対照より柔らかい。 ＋１ 対照よりやや柔らかい。 ０ 対照と同じ。 −１ 対照の方がやや柔らかい。 −２ 対照の方が柔らかい。[Flexibility Test Method] A commercially available cotton towel was repeatedly washed 5 times with a commercially available detergent attack (manufactured by Kao Corporation) to remove the detergent attached to the cloth, and then 1 kg of the above-treated cotton towel was obtained. On the other hand, using 1 g of powdered softener, 3.5 ° DH hard water, 25 ° C., bath ratio 1/30
The mixture was stirred for 5 minutes. The above treated cloth was air-dried at room temperature and then left in a constant temperature and humidity room at 25 ° C. and 65% RH for 1 day.
Regarding the above treated cloths, a pair of comparisons were made on the softness with a cotton towel treated with a commercially available softening agent (Hamming 1/3; manufactured by Kao Co., Ltd.) so that the softening base had the same treatment concentration, and the following evaluations were made. It was evaluated according to the standard. +2 Softer than the control. +1 Slightly softer than the control. 0 Same as control. -1 The control is slightly softer. -2 The control is softer.
【００４０】実施例２ 次式で表される化合物（ＡＢ−２１）をモノステアリル
アミン（ＣＨ3(ＣＨ2)17ＮＨ2)と開環アミド化反応させ
た後、ラウリン酸クロライド（ＣＨ3(ＣＨ2)10ＣＯＣ
１）と反応させ、得られた化合物を水酸化ナトリウム水
溶液で洗浄することにより得られたジ長鎖型第３級アミ
ン化合物にポリビニルアルコールをジ長鎖型第３級アミ
ン酸塩１００重量部に対して１０重量部となるように供
給し、（株）エバラ製作所製のラボ用マイルダーで混合
後、グリコール酸を中和等価量になるように供給し同様
にマイルダーで中和を行った。中和温度は１３０℃に保
った。次いで大川原化工機（株）製のスプレークーラー
（ＣＬ型）に供給し、冷却するとともに中和物を粉末化
させ、ジ長鎖型第３級アミングリコール酸塩の粉末を得
た。次いで、実施例１と同様の評価を行った。得られた
結果を表１に示す。Example 2 A compound (AB-21) represented by the following formula was subjected to a ring-opening amidation reaction with monostearylamine (CH 3 (CH 2 ) 17 NH 2 ), and then lauric acid chloride (CH 3 ( CH 2 ) 10 COC
1) and the obtained compound was washed with an aqueous solution of sodium hydroxide to obtain a di-long chain type tertiary amine compound, and polyvinyl alcohol was added to 100 parts by weight of the di-long chain type tertiary amine acid salt. The amount was 10 parts by weight, and after mixing with a laboratory milder manufactured by Ebara Seisakusho Co., Ltd., glycolic acid was supplied in a neutralization equivalent amount and neutralized with the milder in the same manner. The neutralization temperature was maintained at 130 ° C. Then, the mixture was supplied to a spray cooler (CL type) manufactured by Okawara Kakoki Co., Ltd., cooled, and the neutralized product was pulverized to obtain a powder of dilong-chain type tertiary amine glycolate. Then, the same evaluation as in Example 1 was performed. The results obtained are shown in Table 1.
【００４１】[0041]
【化５】 [Chemical 5]
【００４２】実施例３ 溶解助剤としてグリコール酸と炭酸水素ナトリウムとを
ジ長鎖型第３級アミン酸塩１００重量部に対して各々１
０重量部用いた以外は、実施例１と同様にして行った。
得られた結果を表１に示す。Example 3 Glycolic acid and sodium hydrogen carbonate as solubilizing agents were each added to 1 part of 100 parts by weight of a dilong-chain type tertiary amine acid salt.
Example 1 was repeated except that 0 part by weight was used.
The results obtained are shown in Table 1.
【００４３】実施例４ 溶解助剤としてポリオキシエチレンアルキルエーテル
（アルキル鎖の炭素数１８、酸化エチレン付加モル数１
０）をジ長鎖型第３級アミン酸塩１００重量部に対して
２０重量部用いた以外は、実施例２と同様にして行っ
た。得られた結果を表１に示す。Example 4 Polyoxyethylene alkyl ether as a dissolution aid (having 18 carbon atoms in the alkyl chain and 1 mole of ethylene oxide added)
Example 2 was repeated except that 20 parts by weight of 0) was used with respect to 100 parts by weight of the di-long-chain type tertiary amine acid salt. The results obtained are shown in Table 1.
【００４４】比較例１ １３０℃に昇温した合成例１で得られたジ長鎖型第３級
アミン化合物と、３５重量％の塩酸水溶液を中和等価量
になるように（株）エバラ製作所製のラボ用マイルダー
に供給し温度を１３０℃に保って中和した。次に、５０
〜１００Ｔｏｒｒの圧力下にある日東機器（株）製のス
プレイドライヤー（ＳＤ型）に供給し、水を除去すると
ともに中和物を粉末化させ、ジ長鎖型第３級アミン塩酸
塩の粉末を得た。次いで、深江工業（株）製の転動造粒
機にジ長鎖型第３級アミン塩酸塩の粉末を３ｋｇ、その
粉末１００重量部に対して尿素及びポリエチレングリコ
ールが各１０重量部となるように供給し造粒を行った。
次いで、実施例１と同様に評価した。Comparative Example 1 The dilong-chain type tertiary amine compound obtained in Synthesis Example 1 heated to 130 ° C. and a 35 wt% hydrochloric acid aqueous solution were adjusted to neutralization equivalent amounts so that Ebara Seisakusho Co., Ltd. It was supplied to a laboratory milder manufactured by Kuraray Co., Ltd. and the temperature was kept at 130 ° C. for neutralization. Then 50
It is supplied to a spray dryer (SD type) manufactured by Nitto Kikai Co., Ltd. under a pressure of -100 Torr to remove water and powderize the neutralized product to obtain a powder of dilong-chain type tertiary amine hydrochloride. Obtained. Then, in a rolling granulator manufactured by Fukae Kogyo Co., Ltd., 3 kg of the powder of the di-long-chain type tertiary amine hydrochloride was added, and urea and polyethylene glycol were each added to 10 parts by weight per 100 parts by weight of the powder. And granulated.
Then, the evaluation was performed in the same manner as in Example 1.
【００４５】[0045]
【表１】 [Table 1]
【００４６】表１の結果から判るように、実施例１〜４
の製造方法により得られたジ長鎖型第３級アミン酸塩粒
子は、保存安定性（ケーキング度）、溶解時間、柔軟性
ともに比較例に比べ良好であった。As can be seen from the results in Table 1, Examples 1 to 4
The di-long-chain type tertiary amine acid salt particles obtained by the production method of 1. were better in storage stability (degree of caking), dissolution time, and flexibility than the comparative examples.
【００４７】[0047]
【発明の効果】本発明のジ長鎖型第３級アミン酸塩粒子
の製造方法によれば、流動性に優れ且つ水中での分散性
及び溶解性に優れたジ長鎖型第３級アミン酸塩粒子が得
られる。また、柔軟剤製品応用上の幅広い展開（粉末
型、錠剤型、シート状等）が可能となる。EFFECT OF THE INVENTION According to the method for producing particles of a di-long chain type tertiary amine acid salt of the present invention, a di-long chain type tertiary amine having excellent fluidity and dispersibility and solubility in water is excellent. Acid salt particles are obtained. In addition, a wide range of applications (powder type, tablet type, sheet type, etc.) for softener products can be achieved.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｄ０６Ｍ 101:06 Continuation of front page (51) Int.Cl. 6 Identification number Office reference number FI technical display area // D06M 101: 06
Claims (4)
鎖型第３級アミン化合物の融点ないし沸点の温度範囲で
中和反応を行い、得られたジ長鎖型第３級アミン酸塩と
溶解助剤をジ長鎖型第３級アミン酸塩の融点ないし沸点
の温度範囲で溶融混合し、次いで粉末化することを特徴
とするジ長鎖型第３級アミン酸塩粒子の製造方法。1. A di-long-chain type tertiary amine compound obtained by neutralizing a di-long-chain type tertiary amine compound and an acid in the temperature range of the melting point or boiling point of the di-long-chain type tertiary amine compound. Di-long-chain type tertiary amine acid salt particles, characterized in that an amine acid salt and a dissolution aid are melt-mixed within a temperature range of a melting point or a boiling point of the di-long chain type tertiary amine acid salt, and then powdered. Manufacturing method.
をジ長鎖型第３級アミン化合物の融点ないし沸点の温度
範囲で溶融混合した後、該温度範囲で酸と中和反応さ
せ、次いで粉末化することを特徴とするジ長鎖型第３級
アミン酸塩粒子の製造方法。2. A di-long chain type tertiary amine compound and a solubilizing agent are melt-mixed in a temperature range of a melting point or a boiling point of the di-long chain type tertiary amine compound, and then neutralized with an acid in the temperature range. And then pulverizing, followed by a method for producing di-long chain type tertiary amine acid salt particles.
ルコール、長鎖脂肪酸及びそのエステル化合物、無機塩
及び無機物、有機物及び有機塩、有機高分子、および粘
土鉱物からなる群より選ばれる一種又は混合物である請
求項１又は２記載の製造方法。3. The solubilizing agent is selected from the group consisting of nonionic surfactants, polyhydric alcohols, long-chain fatty acids and their ester compounds, inorganic salts and inorganic substances, organic substances and organic salts, organic polymers, and clay minerals. The method according to claim 1 or 2, which is one or a mixture.
に対して溶解助剤を１〜１００重量部含有し、且つ重量
平均粒子径が５０〜１０００μｍで、見掛け比重が１５
０〜１２００ｇ／リットルである、請求項１、２又は３
記載の方法により製造されるジ長鎖型第３級アミン酸塩
粒子。4. A solubilizing agent is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of a dilong-chain type tertiary amine acid salt, a weight average particle diameter is 50 to 1000 μm, and an apparent specific gravity is 15.
It is 0-1200 g / liter, Claim 1, 2 or 3
Di-long chain type tertiary amine acid salt particles produced by the method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29447393A JP3320173B2 (en) | 1993-10-29 | 1993-10-29 | Di-long chain type tertiary amine salt particles and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29447393A JP3320173B2 (en) | 1993-10-29 | 1993-10-29 | Di-long chain type tertiary amine salt particles and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07126230A true JPH07126230A (en) | 1995-05-16 |
| JP3320173B2 JP3320173B2 (en) | 2002-09-03 |
Family
ID=17808234
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29447393A Expired - Fee Related JP3320173B2 (en) | 1993-10-29 | 1993-10-29 | Di-long chain type tertiary amine salt particles and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3320173B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392346A (en) * | 2011-06-28 | 2012-03-28 | 东华大学 | Method for finishing nano anti-ultraviolet and antibacterial hydrophobic fabrics |
| CN109985564A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | The mixed system and preparation method thereof of fatty acid type surfactant |
-
1993
- 1993-10-29 JP JP29447393A patent/JP3320173B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102392346A (en) * | 2011-06-28 | 2012-03-28 | 东华大学 | Method for finishing nano anti-ultraviolet and antibacterial hydrophobic fabrics |
| CN109985564A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | The mixed system and preparation method thereof of fatty acid type surfactant |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3320173B2 (en) | 2002-09-03 |
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